Iron-Catalyzed Regioselective C═C Bond Migration and Reductive Deuteration

Area of Science:

• Organometallic Chemistry
• Catalysis
• Organic Synthesis

Background:

• Isomerization reactions are crucial for synthesizing valuable organic compounds.
• Developing efficient catalysts for selective functionalization remains a key challenge in organic chemistry.

Purpose of the Study:

• To report a novel iron catalyst, Cp*Fe(Ph2PN=C5H4N), for promoting the rearrangement of β,γ-unsaturated carbonyls.
• To enable regioselective C═C reductive deuteration of these rearranged compounds.
• To synthesize diverse α,β-dideuterated organic molecules.

Main Methods:

• Utilized a well-defined multifunctional iron catalyst, Cp*Fe(Ph2PN=C5H4N).
• Investigated the rearrangement of β,γ-unsaturated ketones, esters, and amides.
• Performed regioselective C═C reductive deuteration using D2.
• Conducted mechanism studies to understand C═C bond relocation and D2 activation.

Main Results:

• The iron catalyst successfully promoted the rearrangement of β,γ-unsaturated ketones, esters, and amides to their α,β-isomers.
• Achieved regioselective C═C reductive deuteration, yielding α,β-dideuterated products.
• Demonstrated broad substrate compatibility under mild reaction conditions.
• Gained mechanistic insights into the catalytic process.

Conclusions:

• Cp*Fe(Ph2PN=C5H4N) is an effective catalyst for isomerizing unsaturated carbonyls.
• The developed protocol provides a versatile route to α,β-dideuterated organic compounds.
• Mechanism studies elucidated the key steps of C═C bond migration and deuterium activation.